Fired photographically decorated ob-



Aug. 18, 1959 A. E. CHARLTON 2,900,255

FIRED PHOTOGRAPHICALLY DECORATED OBJECTS r AND THEIR MANUFACTURE Filed Feb. 18. 1955 H2 H4 ll6 g [24 60 J /62 Opaque Transparent portion portion Negative p q Negative Transparent '8 gm portion 22 portion l6 coating 9?zgqspz'i't'igpfi$34 39;? 3

Plgmenfed 0000 A. o ggg gzgfig light sensitive Sealer co ating coming fl "l4 containing ux l t Light sensitive M Cel'umlc Ware couimg v Fireable ceramic were w EXPO E I I sensitive Image Image coating Pigmentedflight |40 sens! we can m r 22am? f A {a I confine Light sensitive V I ceramic wa e Fireable ceramic ware WASH WASH Image i600 I Image Fireable ceramic l2 -Sealer coating ware IO' -Fireable ceramic ware GLAZE lma e ransparent glaze I 32 Fireable ceramic 0 ware 2 Sealer coating |Q Fireable ceramic ware FIG. 3

FIRE

ir INVENTOR.

Plmented image 1 l 32-, -Transparent ALEXANDER E. CHARLTON glaze y Flreable ceramic ware 6 FIG. 2 A TQ N United States Patent FIRED PHOTOGRAPHICALLY DECORATED OB- JECTS AND THEIR MANUFACTURE Alexander E. Charlton, Cincinnati, Ohio, assignor to Photoceramics, Inc., Cincinnati, Ohio, a corporation of Ohio Application February 18, 1953, Serial No. 337,500

26 Claims. (Cl. 9634) This invention relates to applying colored images and designs photographically to objects to be decorated and the photographically decorated objects, such as ceramic ware, porcelain, glass, porcelain-enamel, metal and the like, and it particularly pertains to colored images and designs which are photographically applied to objects, or portions thereof, provided with separately applied layers of light sensitive coating, the foundation layer of said coating being free from coloring material and the superimposed layer of the coating containing colored material. The image or design is formed in the light sensitive coating and covered with a protective material that is mixed with the coloring material in the superimposed light sensitive layer or applied as a separate layer over the design.

This case is a continuation-in-part of my application Serial No. 162,754, filed May 18, 1950, and now abandoned.

Heretofore images and designs have been applied by a silk screen, transfer processes, rubber stamping, hand applications and in various other ways. If the images or designs have-been applied photographically in light sensitive compositions, they have been applied in a single layer. of light sensitive material. I

Theinvention pertains to applying the designs to the object over or-under.a glazed surface, and if the objects to be" decorated are a biscuitof bisque of a porous nature, the object, or the. portion thereof, to be decorated, is first coated with a 'sealing layer to prevent the subsequently applied light sensitive coating from being ab sorbed into the object. The sealing layer may be a water-soluble material to be washed off and removed with that portion of the light sensitivecoating which is not exposed to the light, as hereinafter described, or it may be water-insoluble material to be retained on the object untilthe' decorated object is heat treated for fusing the design, ifthe object is already glazed, or to glaze both znaazss 2 simplified method for applying designs, with equal facility, either underglaze or overglaze.

A still further object of the invention is to provide a method of photographically applying designs on green or unfired ceramic Ware so that the prepared decorated ware can be produced in onefiring operation.

A still further object of the invention is to provide a photographic process, for decorating objects with designs in different colors, which is more simple and economical than the above mentioned processes.

Further'objects, and objects relating to details of construction and economies of operation, will readily appear from the detailed description to follow. In one instance, I have accomplished the objects of my invention by the devices and means set forth in the following specification. My invention is clearly defined and pointed out in the appended claims. Structures constituting preferred embodiments for carrying out my invention are illustrated in the accompanying drawings, forming a part of this specification, in which:

Fig. l is a schematic view of a production line set-up to practice my invention.

Fig. 2 is a sectional view, greatly enlarged, illustrating the various steps of my process for underglaze applications.

Fig. 3 is a sectional view similar to Fig. 2 but illustrating the various steps of my process as applied to porcelain, glazed ceramics, glass, porcelain-enamel,

' metallic surfaces and the like.

the object'and the design if said object is a biscuit that has not previously been fired to glaze its surface.

The principal object of the present invention is a photographically decorated object without objectionable shaded background and with the decoration set out clearly and distinctly in sharply defined lines oroutlines, and a method of so decorating the object.

Another object of the invention is to form the design in a light sensitive coating applied to the object in separate layers,- the-underlayer of-said coating being free from. coloring matter andthe overlayer thereof containingcololfingmatter.

Another object of the invention is to have the' light sensitive material of a character normally soluble in a suitable solvent, such as water, but which,. upon exposure to light,'is hardened and insolubilized so that the portions which have not been exposed to the .light in formingthe design can be readily removed by. the solvent, leaving the hardened'and insolubilized design portions' intact.

. A further object, of the inventionis to provide a Generally described, the invention pertains to fired photographically decorated objects, glazed or unglazed, in which the decoration is formed in light sensitive coating material, said coating being in separately applied layers with the overlayer containing coloring material and the underlayer being free from coloring material. The multiple layer light sensitive coating prevents objectionable colored background and sets oif the decoration design in sharp well-defined outline.

' Referring specifically to the drawings in which like numerals are used to designate like parts, numeral 10 (Fig. 2) denotes generally an unglazed ceramic biscuit or bisque. The biscuit is preferably thoroughly heated to a temperature of about 200 F. in any suitable way, such as in oven 11 shown in Fig. 1.

Since the ceramic biscuit is porous, it, or the surface to be decor'ated, is coated with a sealing composition 12, which preferably will not be absorbed into the biscuit, and is applied upon the upper surface of the object in any suitable manner, such as by spraying, to provide a smooth base surface for. a subsequently applied light sensitive coatingwithout absorption of said light sensitive coating into the biscuit. The sealer is preferably dyed to give it some color for enabling the operator to determine and regulate the degree or amount of sealer to be applied. No sealer, of course, is necessary if the article to be decorated is not of ,a porous absorbent character, such as when the article has been already glazed previously to being decorated. Any suitable sealing material can be used, it being such to be burned oif during the subsequent firing of the decorated object, or .of the decorated design applied thereto, without leaving any appreciable residue, and will not affect the subsequently appliedlight sensitive coating'and any glaze for the decorative design.

The sealing material maybe of ahydrophilicor hydrophobic nature, depending whether or not it, or a portion thereof, is to be washed off and removed prior to the subsequent firing. I-lydrophilic sealing material'is typified by any number of materials, with or without a dye mixed therewith. Such sealing materials are represented by water soluble glue; gelatin; natural gums and resins, such as gum arabicand gum tragacanth; glucose; cellulose derivatives, such as methycellulose, hydroxyethyl cellulose,

sodium carboxymethyl cellulose, cellulose ethers; watersoluble derivatives of hydrolyzed polyvinyl acetate, such as, polyvinyl alcohol; Water-soluble derivatives of glycols, such as polyalkylene'glycols', preferably of a molecular weight of over 1000.

A preferred sealingxmaterial is amethyl cellulose derivative which after it is set is insoluble in hot water, but is soluble in cold Water. A suitable'specific example comprises 5 grams of a Water-solubledye dissolved in 400 0.0. of a 3% solution of methocel of 100 centipoise viscosity. Methocel is a methyl cellulose material mari ufactured and sold by Dow Chemical Company.

Hydrophobic sealing materials are typified .by water-. insoluble natural resins and gums, such as shellac, lacquer; Water-insoluble synthetic acrylate resins, such as, methyl acrylate, methyl methacrylate, polymethyl acrylate, polyethyl acrylate, polystyrene resins, polyvinyl acetates, polyvinyl chloride-acetates, polyvinyl acetals, coumaroneindene resins, rosin modified maleicester resins, chlorinatecl parafiins, polyisobutylenes, phenolic resins, urea and chlorinated rubbers, water-insoluble derivatives of cellulose, such as methyl cellulose, cellulose nitrate, cellulose ethyl ether and nitro cellulose lacquers. Nitro celulose lacquer is preferred.

All of the above sealing materials are by way of examples for generally designating their general character and function, the sole purpose of the sealing material being to provide a temporary foundation layer on the object to be decorated to prevent penetration therein of the light sensitive material, and Which sealing material is subsequently removed by Washing with water or solvent and/ or by firing. The use of the sealing material is optional, and used only if the object to be decorated is porous or absorbent.

The sealing layer 12 is overlaid with light sensitive coating of any suitable material which is of hydrophilic or hydrophobic character and is of a colloidal or resinous nature. Suitable hydrophilic light sensitive materials are typified by any of the following representative examples:

Formula #1:

Zinc chloride double salt of the diazo compound of 4 amino 1(N methyl G-naphthalenetetrahydride-1.2.3.4) aminobenzene grams 0.8 Acetic acid50% solution cc 2 Formula #6:

Distilled water cc 130 Gelatin gra1ns 10 Diazo compound of 4-amino-2-carboxy-1 N-phenyl 4-amino-4'-hydroxy-1.1'-diphenylmethane grams 1 Sodium 1.3.6 naphthalene-trisulfonate do 2 Acetic acid-50% solution cc- 2 Formula #7:

Distilled water cc 50 Methylcellulose2% solution cc 50 Diazo compound obtained by condensing paraformaldehyde with the sulfate of 4-diazo-l.1 dipheneylene grams 0.5 Citric acid do 0.7

Formula #8:

Distilled water cc 100 Process glue cc 30 Diazo compound as in Formula #7 grams 0.6 Citric acid do 0.7

Formula #9:

Distilled water cc 40 Resin obtained by the condensation of urea-aldehyde, containing about 15% solid urea cc 4-0 Ammoniumdichromate15% solution cc l0 Albusol cc 0.5 Copper bromide 10% solution cc 0.5

Formula #10:

Distilled water cc Polyacrylic acid.-l0% aqueous solution cc- 20 Potassium bichromate-10% solution cc 15 All of the above ten examples of-the hydrophilic light sensitive emulsion materials are the typewhich canbe developed with water of varying temperature. This means that when exposedto a light source through a photographic negative or positive, the light will act upon the exposed portion of the light sensitive material to harden or water-insolubilize i-tthereby'permitting the non-exposed portions thereofwhich are not hardened or insolubilized to be dissolved and removed by the application of Water'of'varying degrees of temperature. Because of manufacturing economics, the hydrophilic light sensitive emulsions are preferred to hydrophobic ones in carrying out this invention.

There are many other types of 'hydrophiliclight sensitive emulsions which can be used, such as'the Wellknown silver halide-gelatin emulsions as described'in Bassist, Patent No. 2,344,487 and Tuttle'2,600,343 and the silver halide-gelatin-resin emulsion described in Yackel et al., Patent No. 2,607,683.

Suitable hydrophobic light sensitive colloids and resins are represented by the following examples, these depending for their development upon the application of a nonaqueous solvent therefor:

Formula #11:

Distilled water cc 500 Orange shellac grams 50 Ammonium carbonate do 10 Ammonium bichromate grains 35 Ammonia (concentrated) cc 15 The above is developed by an 80% solution of denatured alcohol.

Formula #12:

Benzene cc 30 Solvent naptha cc 15 Ethyl methyl ketone cc 20 Gum varnish cc 25 Asphaltum 'grams 3 Lead triethyl iodide do 4.2 Iodoform do 3 The above is developed with turpentine.

Formula #13:

Benzyl aniline f grams 35 Formaldehyde40%" solution cc' 8 Distilled water cc 4 Hydrochloric acid (concentrated) drops.. 2

' These are mixed and heated in a reflux condenser for one hour. Y

The above is developed with a xylene-toluene mixture;

The light sensitive coating material is not limited to the specific examples above given as many other colloidal and resinous substances combined with sensitizing mediums are well-known, the above being merely representative of some of many which are suitable for carrying out the invention. i

The light sensitive'coating. is applied in two layers 14 and 16,. layer 14 being first applied "and thenoverlaid with layer 16 after the first layer 14 has dried. Layer 14 may be any of the above mentioned light sensitive compositions, or others, without any coloring material incorporated therewith, whereas layer 16 is light sensitive with coloring material included therewith. The layer 16 is preferably of the same light sensitive material as layer 14 but not necessarily so as it may, of course, be of any light sensitive material. For example, I make up the following solutions as follows:

Solution B is then poured'into solution A, and the two solutions are mixed together. The resulting combined solution is heated and maintained at a temperature of about 120 F. at which temperature it can be applied as a very fine spray to form the layer 14. For

best results, it is imperative that the layer 14 completely cover the sealing layer 12. It will solidify immediately upon contact with the heated biscuit, which should be may be formed of any light sensitive material, preferably of the same material as that for the non-pigmented layer 14. The pigment for coloring the pigmented light sensitive material 16 is preferably free from flux.

To each 120 cc. of the bichromated colloid formed by mixing solutions A and B, 40 grams of ceramic pigment and 30 cc. of distilled water are added, the resultant pigmented bichromated colloid being sprayed upon layer 14 ata temperature of about 70 F., while maintaining the surface of the biscuit at a temperature of approximately 140 F., to form the layer 16. This layer 16 should be uniformly applied andno thicker than is necessary toobtain the desired result. I have found that if just enough of the pigmented light sensitive coating is applied to obtain opacity, excellent results will be assured.

Utilization of the intermediate non-pigmented light sensitive layer 14 between the sealing layer 12 and the pigmented light sensitive layer 16 (in underglaze application), and the provision of this layer 14 between the upper surface of the glazed biscuit or the upper hardened surface of porcelain, glass, metal and the like, and beneath the pigmented light sensitive layer 216 (Fig. 3) results in the provision of a protective coating or layer which effectively precludes the pigment, carried in the 6 pigmented light sensitive coating 16 and 216, from coin ing into actual contact with the outer surface of the article being decorated, thereby efiectively eliminating objectionable background color. The light sensitive layer 14 is an intermediate layer interposed between the pigmented light sensitive layer 16 and 216 and'the object being decorated, or the sealing layer 12 thereon if said sealing layer 12 be employed. In this manner, a clean well defined line of demarkation is provided between the exposed, hardened portions of the non-pigmented light sensitive layer 14 and of the pigmented light sensitive layer 16 and 216, and the non-exposed portions of each of these layers are of such a nature that the non-exposed portions of each can be readilywashed away, thereby leaving the exposed portions 140, 160 and 1600 intact with cleanly defined edges. v

The ceramic biscuit-as above described is ready for exposure to light for forming the design in the light sensitive layers. A negative 18 having opaque portions 20 and transparent portions 22 is placed upon and in abutting relation with the upper surface of the pigmented light sensitive layer 16; and the light sensitive layers 14 and 16 are exposed by subjecting the ceramic biscuit and the negative to the action of an actinic light source 24, Fig. 1. Excellent results have been obtained with an exposure period of about seconds, using a bank of commercially available 360 BL fluorescent black light lamps, such as are manufactured by the General Electric Company, at a distance of 1 /2 inches.

Exposure to actinic light will result in those portions of the layers 14 and 16 which are beneath the'transparent portions 22 of the negative being acted on by the actinic light, whereby the coatings will become quite hard and insoluble, as denoted by the numerals 140 and 160. These portions of the layers 14 and 16 which are beneath the opaque portions of the negative, and consequently not affected by the actinic rays of light, are not hardened and insolubilized but remain soluble.

After the exposure period, the biscuit of Fig. 2 may then be sprayed with warm water at temperatures ap proximating to F., whereby the unexposed portions of the layers will be washed away, leaving only the hardened light exposed portions 140 and of the layers 14 and 16 adhering to the biscuit. It will be noted that in some instances, the washing operation may likewise remove a part of the outer surface of the sealer coating 12 not underlying the hardened portions 140 and 160, as indicated by broken lines 30, if the sealing layer 12 is water-soluble. However, this is not detrimental to the products so long as there is no substantial undercutting beneath said hardened portions. -It is, of course, immaterial whether or not any of this sealing layer, beneath the unhardened portions, be Washed away inasmuch as it or any remaining part will be subsequently removed in the firing operation together with the part beneath the hardened portions. If it be water-insoluble, none Will be washed away but removed entirely by the firing operation. Likewise a water-soluble sealer can be entirely removed in-the firing operation.

vWhere the sealing material is of water-soluble material, care should be exercised in washing the non-exposed Water-soluble portions of layers 14 and 16 to prevent sub.- stantial undercutting into the side edges of that part of ,the layer 12 whichjis immediately beneath the portions .140 and 1600f the twolight sensitive layers 14 and 16. The degree of removal as denoted by the broken lines 30 of the top surface portionof thesealing layer 12 may-be accurately controlled bycontrollingthe temperature and pressure of the washing water 'as; well asthe length of time during which the object is exposed to the action of the wash water. a

With reference now to Fig. 1, I have illustrated a typical set-up suchas may be used in practicing my process one h g e fic encytnm production basis.- '.The,n meral 7 50 denotes generally anendless conveyor on which the ceramic biscuits may be suitably supported while being subjected to the various steps of my process.

The biscuits may be suitably heated to about 200 degrees Fahrenheit in an oven denoted generally by the numeral 11. The biscuits 10 are then sequentially passed beneath spraying devices denoted generally by the numerals 112, 114 and 116 wherein a sealer solution 12 at approximately 120 F. is discharged from unit 112; a bichromated colloid solution 14 at approximately 120 F. is discharged from unit 114; and a pigmented bichromated colloid 16 at about 70 F. is discharged from unit 116. It will be observed that the thickness of various coatings thus applied may be accurately controlled whereby the thickness of coatings 12, 14 and 16 will be uniform and even for each and every biscuit. Suitable means, not illustrated, may be utilized for maintaining the biscuit temperature at-approximately 140 F.

The numeral 118 denotes generally a stack of negative or positive transparencies 18, one of which is placed on top of the bichromated pigmented coating 16 of each biscuit prior topassage of the biscuit beneath the action of a battery'of lights 24, preferably rich in actinic rays. After exposure the negatives or positives may be removed at the station indicated by the numeral 60, it being noted that the negatives may then be replaced in stack 118 for re-use. After the negatives or positives have been removed, the biscuits are then caused to pass beneath a battery of spray-heads denoted generally by the numeral.

62,'from which warm water at temperatures about 120 to 140 F. is sprayed for the purpose of removing those portions of the bichromated coatings 14 and 16, which were not exposed to the hardening action of the actinic rays. The biscuits upon arrival at the discharge end 64 of the conveyor may then be suitably dried preparatory to spraying with a glaze 32 (Fig. 2) and firing.

It should be understood that the apparatus disclosed in Fig. 1 is suggestive only and that various changes therein could be made, such as, by way of example, the various coatings could be rolled or whirled on instead of being sprayed, as illustrated. It should likewise be noted that suitable means are to be provided for insuring a good contact between adjacent portions of negatives or positives 18 and coating 16 (and 216) whereby to obtain a clear, clean exposure of the sensitized coatings.

In those instances where it is desirable to decorate green ware, which term denotes a mass of ceramic material which has been formed to a certain shape but which has not been baked, the same steps illustrated in Fig. 2 may be employed; but with exception of the characteristics of sealer coating 12. When working with green ware, it shown be sealed in its entirety, or in its outer surface in the case of hollow ware, or at least on those portions to be decorated, with a suitable water-insoluble protective sealer, such as, by way of example, a nitro cellulose lacquer. The characteristics of the protective sealer should be such as to protect the green ware against disintegration during handling and the step of washing off" the non-exposed layers of coatings 14 and 16. The sealer should be of such a nature as to burn off of the ware during firing without leaving objectionable traces of residue.

In those instances when it is desired to utilize my processfor applying my photographic decorating process to overglaze applications, or to glass, porcelain, porcelainenamel, metallic and other hard surfaces,-the steps disclosed in Fig. 3 may be followed.

tical except that thepigmented bichromated coating 216 also contains a-suitable-flux, the purpose of which is to Bichromated colloid as obtained from mixing solutions A and B above) cc Distilled water cc 30 Pigment grams 10 Flux do 30 If desired, commercially available pigmented fluxes may be utilized and mixed with a bichromated colloid and distilled water. Such pigmented fluxes may be purchased under such namesas: overglaze colors, glass colors, porcelain-enamel colors, etc.

it should, however, be understood that the proportions and type of the flux and pigment, as well as the other ingredients, may be varied according to. the results desired. By way. of example, if the product to be decorated is to have. a shiny, glass-like finish, the proportions of flux will be increased; however for a dull, unglossy finish, a lesser amount of flux may be used.

The, term flux as used herein refers to a fritted glass ground to a very fine mesh. Different fluxes will have various melting temperatures, thus, for application to glass a flux which would mature at approximately 1000 to 1200 F. would be used; for application to glazed pottery a flux maturing at approximately 1200 to 1400 F. would be used. If porcelain-enamel is to be decorated, a flux maturing at approximately 1350 to 1500" F. would be used.

After the pigmented bichromated colloid coating 216 and the intermediate bichromated coating 14 have been exposed as in Fig. 3, the non-exposed soluble portions may be washed away leaving only the exposed portions and 1600. The base member 10 is then fired at a temperature which will mature the particular flux utilized in coating 1600. When the flux matures, it will bond itself to the surface of member 10, thereby imprisoning the pigment particles in place. It will be understood that the firing operation will carbonize the intermediate bichromated coating 140 and those portions of the pigmented bichromated coating containing the flux 1600 whereby the finished product will contain a deposit of pigment and -fiux 340 which will be permanently bonded to the object.

in those instances wherein my process is used on nonporous porcelain, a pure ceramic pigment may be utilized in the bichromated coating 216 rather than a fluxed pigment, since porcelain is generally covered with a glaze before firing.

Numerous novel effects may be obtained in those instances wherein a fluxed pigment is utilized which has a lower melting point than the glaze for under glaze work. Other novel effects may be obtained by heightening the sealer coat in such a manner as to allow the pigment to spread incident to firing.

be provided with diflerent colors are selectively coated with pigmented bichromated colloids of different colors whereby the entire surface to be decorated will be covered 'with contiguous areas of diflerent colored pigmented bichromated coatings 16 or 216.

The exposure process is the same as when but one color is used, it being understood that the exposure period will fix and convert to a hardened insoluble substance the exposed portions of the various bichromated coatings, and that the non-exposed portions of the bichromated coatand-16 be Washed away by means of water spray 62. Afterdrying, the product may be provided 7 Letters Patent, is:

with a glaze and then fired, or in those instances wherein an undercoating sealer 12 was not utilized, as in Fig. 3, the product is ready for firing whereby the pigmented flux will be bonded to the decorated surface, as in the last step of Fig. 3.

Another method for producing multicolors would be through the use of color separation negatives or positives. With reference to Fig. 2, the biscuit is provided with the sealer coating 12, then the light sensitive coating 14, and the pigmented light sensitive coating 16, containing a pigment of a color which corresponds to the color of the color separation negative or positive to be used. The biscuit as thus prepared is then exposed with this color separation negative or positive, arranged in proper superimposed registration, developed and dried. After being thoroughly dried, the biscuit is then provided with a second layer of the light sensitive coating 14, and also a second layer of a pigmented light sensitive material 16, this layer 16 containing a different color corresponding to another one of the colors of the color separation negatives or positives. The biscuit is then placed in registration With another negative or positive to be again exposed, developed and dried. In this manner as many colors as desired can be superimposed one upon another, each color going through a cycle of the three main steps of the process, which are, emulsion application in the plurality of layers, exposure and development. In such a manner the semi-finished article can be glazed with the transparent glaze 32 and fired as in Fig. 2, or provided with fluxed pigments and fired as in Fig. 3. V I

It should be understood that various changes may be made within the scope of the appended claims without departing from the spirit of the invention. In this connection it should be noted that highly satisfactory results may be obtained using any of the commercially available bichromated colloids whether of the water-soluble or water-insoluble type. I have selected water-soluble bichromated colloids since they lend themselves more readily to highly efficient, inexpensive mass production techniques, however I do not intend nor Wish to limit my invention to the use of water-soluble bichromated colloids or to any particular light sensitive materials.

In conclusion, it should be observed that the excellent results obtained from my process are attributable to the tive coating immediately beneath and as the support for the upper pigmented light sensitive coating 16 and/or the pigmented light sensitive coating 216 which also contains a flux. l

Experimentation has indicated that highly successful results may be obtained when decorating glazed ware when using a pigmented light sensitive coating characterized by an absence of flux therein, as coating 16. Such a pigmented light sensitive coating, when fired at a temperature equal to or greater than the melting point of the glaze, will result in the pigmented portion of the design becoming imbedded, as it were, in the glaze whereby the outer surface of the resultant product will be substantially uniform and co-planar.

At this point it should be noted that in those instances wherein a flux is used in the pigmented light sensitive coating 216 (Fig. 3) the resultant design is literally superposed upon the outer surface of the glaze similar to an engraving.

I am aware that there may be various changes in details of construction without departing from the spirit of my invention, and, therefore, I claim my invention broadly as indicated by the appended claims, it being understood that the invention is notlimited to the use of any particular sealings, if any be used at all,,or to the use of any particular light sensitive material in forming the multiply light sensitive layer.

Having thus described my invention, what I claim as new and useful and desire to secure by United States decorated with non-pigmented organic colloidal light sensitive coating, overlaying said coating with an-organic' colloidal light sensitive coating containing a fireable pigment, exposing a portion of said coatings to a design image defined by a light source to cause the exposed and unexposed portions to be in contrast as to hardness and solubility in a solvent for the light sensitive material, re-

moving the non-image carrying portions from the light sensitive coatings for leaving intact on the fireable material to be decorated only the design image, and then firing said material with the retained design image thereon to form a finished decorated product.

2. The method of claim 1 in which the material to be decorated is first coated with a sealant.

3. The method of claim 2 in which the non-image carrying portions are removed with a solvent.

4. The method of photographically decorating products comprising coating that portion which is to be decorated with an organic colloidal light sensitive material to provide an undercoating, superimposing an organic colloidal light sensitivematerial overthe undercoating, the superimposed material containing fireable pigment and the undercoating being non-pigmented exposing a portion of said coatings to an image defined by actinic light.

for hardening said light exposed portion, washing away the non-exposed, unhardened portion of the coatings with material which is solvent to them but is not solvent as to the hardened portions, and bonding the pigment image of the hardened portions in place.

5. The method of photographically decorating products as set forth in claim 4 in which a sealant coating is first applied to the surface to be decorated beneath the subsequently applied light sensitive coatings.

6. The method of photographically decorating fireable materials with a pattern of fireable pigment which method comprises the steps of providing those portions to be decorated with a bichromated organic colloidal light sensitive coating free of fireable pigment, and of then applying to said first coating a second light sensitive coating containing a fireable pigment and a flux, of exposing said coatings to an image for hardening the exposed portions of said coatings, of washing away the nonexposed portions of each of said coatings for-leaving intact on the material only the exposed portions .of said coatings, and of then firing said material to form a finished decorated product.

7. The method of photographically decorating fireable materials including ceramic ware, porcelain, glass, porcelain-enamel,metallic surfaces, and the like which method comprises the steps of providing those portions to be decorated with a bichromated organic colloid coating characterized by an absence of fireable pigment, and of then applying to said first coating a bichromated organic colloid coating containing a fireable pigment and a flux, of exposing said coatings to an image for hardening the exposed portions of said coatings, of washing away the non-exposed portions 'of each of said coatings for leaving intact on the material only the exposed portions of said coatings, and of then firing said material to form a finisheddecorated product. H

8. The method of decorating green ware which com prises the steps of coating at least those portions of the ware to be decorated with a water insoluble protective sealer coating which will burn off the ware during firing thereof leaving no organic solids, of applying a water soluble bichromated organic colloid coating free of fireable pigment-to said sealer coat, of then applying a water soluble fireable pigmented bichromated organic colloid coating to said bichromated colloid organic coating, of exposing said coatings to an image for hardening the exposed portions ofsaidlast two mentioned coatings, of

11 washing away the non-exposed portions of said bichromated andsaid pigmented bichromated coating for leaving intact'on the green ware only the exposed portions of said coatings, and then glazing and firing said ware to form a finished decorated ceramic product which has been fired but once.

9. The method of photographically decorating a metallic surface which comprises the steps of providing the surface with a coating of a bichromated organic colloid, free of fireable pigment and of then applying to said coating a bichromated organic colloid coating containing a fireable pigment and a flux, of exposing said coatings to an image for hardening the exposed portions of said coatings, of washing away the non-exposed portions of each of said coatings for leaving intact on the metallic surface only the exposed'portions of said coatings, and of then firing the metallic product to eifect a permanent fusing of the pigment to said surface.

10. The method of decorating unglazed ceramic ware which comprises the steps of sequentially coating the ware with a water soluble surface-sealing coating capable of being burned off the ware during firing, and a bichromated organic colloidal coating containing a fireable pigment, exposing said coatings to an image, washing away the non-exposed portions of said bichromated coatings for leaving intact therein the exposed portions, then glazing and firing said ware to form a finished ceramic prodnet.

11. The method of decorating unglazed ceramic ware which comprises the steps of thoroughly pre-heating said ware to about 200 degrees Fahrenheit, then applying a thin coating of a colloid capable of being burned ofr the ware during firing, applying a water soluble, organic bichromated colloid free of fireable pigment, then applying a water soluble organic bichromated colloid containing a fireable pigment, exposing the coatings to an image, Washing away the non-exposed portions of said bichro- 'mated coatings for leaving intact therein the exposed portions, then glazing and firing said ware to form a finished ceramic product.

12. The method of decorating unglazed ceramic ware which comprises the steps of thoroughly heating said ware to about 200 degrees Fahrenheit, then applying a thin,

even sealing coating comprising a colloid capable of being burned off the ware during firing, of applying a water soluble bichromated organic colloidal free of fireable pigment coating at a temperature of about 120 degrees Fahrenheit over the first coating, thenapplying a water soluble bichromated organic colloid containing a fireable pigment to the second coating, exposing said coatings to actinic light under a negative, of flowing water over the Ware for washing away the non-exposed portions of said bichromated coatings for leaving intact those portions of said coatings exposed to the actinic light wherein the temperature of said washing water approximates 120 to 140 degrees Fahrenheit, and then glazing and firing said ware to form a finished ceramic product.

13. The method of decorating glazed ceramic ware which comprises thesteps of providing a water soluble bichromated organic colloidal free of fireable pigment directly onto the glazed surface, of providing a bichromated organic colloidal coating containing a fireable pigment and flux onto said first coating, exposing said coatings to an image, whereby the exposed portions of said water soluble coiloids will become insoluble, of Washing away the non-exposed portions of said coatings, and then firingsaid ware to form a finished, decorated ceramic product.

14. The method of eliminating the presence of undesirable background coloring in the photographic decoration of fireable materials including ceramic ware which comprises the step of providing the ware with a light sensitive bichromate'organic colloidal coating which is characterized by an absence of fireable pigmentimmediately beneath and as the support for a second light sensitive bichromate organic colloidal coating containing a fireable pigment exposing said coatings to an image for fixing the exposed portions of said coatings, washing away the non-exposed portions of said coatings for leaving intact on the ware the said exposed portions, then firing said ware to form a finished, decorated ceramic product.

15. The method of decorating unglazed ceramic ware which comprises the steps of sequentially coating the ware with a surface-sealing coating, a water soluble bichromated organic colloidal coating free of fireable pigment, and awater soluble bichromated organic colloidal coating containing a fireable pigment, exposing said coatings to an image, washing away the non-exposed portions of said bichromated coatings for leaving intact therein the exposed portions, then glazing and firing said ware to form a finished ceramic product.

16. The method of eliminating the presence of undesirable background color incident to the photographic decoration of fireable materials, including ceramic ware, with a pattern of fireable pigment, which method comprises the step of providing the material with a first light sensitive organic colloidal coating free of fireable pigment immediately beneath and as the support for a second light sensitive organic colloidal coating, wherein both of said light sensitive coatings are capable of being burned off the material during the firing operation, and wherein only the second light sensitive coating contains a fireable pigment, exposing said coatings to an image for fixing the exposed portions of said coatings, washing away the non-exposed portions of said coatings for leaving intact on the material the said exposed portions, and then firing said material to form a finished decorated object.

17. The method of eliminating the presence of undesirable background color incident to the photographic decoration of fireable materials, including ceramic ware, with a pattern of fireable pigment, which method comprises the step of providing the material with a first light sensitive organic colloidal coating free of fireable pigment immediately beneath and as a support for a second light sensitive organic colloidal coating, wherein both of said light sensitive coatings are capable of being burned off the material during the firing operation and wherein only the second light sensitive coating contains a fireable pigment, exposing said coatings to an image for fixing the exposed portions of said coatings, removing the non-exposed portions of said coatings for leaving intact on the material the said exposed portions, and then firing said material to form a finished decorated object.

18. A photographically decorated object having the decorated portion provided with a coating composed of a pi mented light reacted sensitized organic colloidal layer superimposed over a non-pigmented light reacted sensitized organic colloidal layer, said decorated portion having a fusible flux incorporated in one of the layers for fusing the decorated portion to said object.

19. The photographically decorated object of claim 18 in which the fusible flux is incorporated in the pigmented layer.

20. The decorated object of claim 18 in which the fusible flux overlies the pigment.

21. A photographically decorated object having the decorated portion provided in a coating of pigmented light reacted sensitized organic colloidal material superimposed over a non-pigmented light reacted sensitized organic colloidal material, and a flux associated with the decorated portion for fusing said decorated portion to the object.

22. A photographically decorated object having the decoratedportionprovided with a design coating having a fireable pigmented light reactive sensitized organic colloidal layer superimposed upon a non-pigmented light reactive sensitized organic colloidal layer, the light sen- SlllZd layers being of a character to be burned away leaving the pigmentin design, and means for bonding the pigment design to the object, said means comprising a fusible flux incorporated in one of said layers;

23. The method of decorating an object comprising applying pigment in the top layer of superimposed layers of light sensitive organic colloidal material, the underlayer next to the pigmented superimposed layer being non-pigmented, light reacting the light sensitive layers to set out the pigment in design, removing the non-light reacted light sensitive material, leaving only the light reacted portions of said layers in design, and firing the pigment to the object for bonding the pigment thereto.

24. The method of photographically decorating objects comprising coating said objects with superimposed layers of light sensitive organic colloidal material, the top layer containing a pigment and the layer next thereunder being free from pigment, exposing said layers to a design defined by a light source for causing the exposed and nonexposed portion of said layers to be in contrast as to hardness and solubility in a solvent for the light sensitive material, removing the non-image carrying portions and the light reacted material in the design for leaving the pigment design intact, and fixing the pigment design to the object.

portion of the object to be decorated a coating of nonpigmented light-sensitive organic colloidal material, applying a coating of pigmented light-sensitive organic colloidal material over the non-pigmented coating, photographically applying a design in said coatings, developing the design in the superimposed coatings, applying over the portion of the object to be decorated a coating of non-pigmented light-sensitive organic colloidal material, superimposing a coating of pigmented light-sensitive organic colloidal material over the non-pigmented coating, the pigment of the successive pigmented coating being of ditierent color, photographically applying a design in said superimposed pigmented coating, developing the design in the superimposed coatings, and bonding said design in place.

References Cited in the file of this patent UNITED STATES PATENTS 223,762 Salvy Jan. 20, 1880 1,265,641 Foerster May 7, 1918 2,215,128 Menlendye Sept. 17, 1940 2,373,732 Wolfson Apr. 17, 1945 2,431,359 Wolfson Nov. 25, 1947 2,472,128 Staehle June 7, 1949 2,685,510 Yackel W; Aug. 3, 1954 

1. THE METHOD OF PHOTOGRAPHICALLY DECORATING FIREABLE MATERIALS INCLUDING CERAMIC WARE, PORCELAIN, GLASS, PORCELAIN-ENAMEL, METALLIC SURFACES, AND THE LIKE, COMPRISING COVERING PORTIONS OF THE FIREABLE MATERIAL TO BE DECORATED WITH NON-PIGMENTED ORGANIC COLLIDAL LIGHT SENSTIVE COATING, OVERLAYING SAID COATING WITH AN ORGANIC COLLOIDAL LIGHT SENSITIVE COATING CONTAINING A FIREABLE PIGMENT, EXPOSING A PORTION OF SAID COATING TO A DESIGN IMAGE DEFINED BY A LIGHT SOURCE TO CAUSE THE EXPOSED AND 